Equilibrium and column studies of iron exchange with strong acid cation resin

The exchange of iron species from iron (III) chloride solutions with a strong acid cation resin has been investigated in relation to a variety of water and wastewater applications. A detailed equilibrium isotherm analysis was conducted wherein models such as Langmuir Vageler, Competitive Langmuir, Freundlich, Temkin, Dubinin Astakhov, Sips and Brouers-Sotolongo were applied to the experimental data. An important conclusion was that both the bottle-point method and solution normality used to generate the ion exchange equilibrium information influenced which sorption model fitted the isotherm profiles optimally. Invariably, the calculated value for the maximum loading of iron on strong acid cation resin was substantially higher than the value of 47.1 g/kg of resin which would occur if one Fe3+ ion exchanged for three “H+” sites on the resin surface. Consequently, it was suggested that above pH 1, various iron complexes sorbed to the resin in a manner which required less than 3 sites per iron moiety. Column trials suggested that the iron loading was 86.6 g/kg of resin when 1342 mg/L Fe (III) ions in water were flowed at 31.7 bed volumes per hour. Regeneration with 5 to 10 % HCl solutions reclaimed approximately 90 % of exchange sites.

An examination of isotherm generation : impact of bottle-point method upon potassium ion exchange with strong acid cation resin

This paper relates to the importance of impact of the chosen bottle-point method when conducting ion exchange equilibria experiments. As an illustration, potassium ion exchange with strong acid cation resin was investigated due to its relevance to the treatment of various industrial effluents and groundwater. The “constant mass” bottle-point method was shown to be problematic in that depending upon the resin mass used the equilibrium isotherm profiles were different. Indeed, application of common equilibrium isotherm models revealed that the optimal fit could be with either the Freundlich or Temkin equations, depending upon the conditions employed. It could be inferred that the resin surface was heterogeneous in character, but precise conclusions regarding the variation in the heat of sorption were not possible. Estimation of the maximum potassium loading was also inconsistent when employing the “constant mass” method. The “constant concentration” bottle-point method illustrated that the Freundlich model was a good representation of the exchange process. The isotherms recorded were relatively consistent when compared to the “constant mass” approach. Unification of all the equilibrium isotherm data acquired was achieved by use of the Langmuir Vageler expression. The maximum loading of potassium ions was predicted to be at least 116.5 g/kg resin.

Ion exchange treatment of saline solutions using lanxess S108H strong acid cation resin

Common to many types of water and wastewater is the presence of sodium ions which can be removed by desalination technologies, such as reverse osmosis and ion exchange. The focus of this investigation was ion exchange as it potentially offered several advantages compared to competing methods. The equilibrium and column behaviour of a strong acid cation (SAC) resin was examined for the removal of sodium ions from aqueous sodium chloride solutions of varying normality as well as a coal seam gas water sample. The influence of the bottle-point method to generate the sorption isotherms was evaluated and data interpreted with the Langmuir Vageler, Competitive Langmuir, Freundlich, and Dubinin-Astakhov models. With the constant concentration bottle point method, the predicted maximum exchange levels of sodium ions on the resin ranged from 61.7 to 67.5 g Na/kg resin. The general trend was that the lower the initial concentration of sodium ions in the solution, the lower the maximum capacity of the resin for sodium ions. In contrast, the constant mass bottle point method was found to be problematic in that the isotherm profiles may not be complete, if experimental parameters were not chosen carefully. Column studies supported the observations of the equilibrium studies, with maximum sodium loading of ca. 62.9 g Na/kg resin measured, which was in excellent agreement with the predictions of the data from the constant concentration bottle point method. Equilibria involving coal seam gas water were more complex due to the presence of sodium bicarbonate in solution, albeit the maximum loading capacity for sodium ions was in agreement with the results from the more simple sodium chloride solutions.

Factors influencing kinetic and equilibrium behaviour of sodium ion exchange with strong acid cation resin

This study reports an investigation of the ion exchange treatment of sodium chloride solutions in relation to use of resin technology for applications such as desalination of brackish water. In particular, a strong acid cation (SAC) resin (DOW Marathon C) was studied to determine its capacity for sodium uptake and to evaluate the fundamentals of the ion exchange process involved. Key questions to answer included: impact of resin identity; best models to simulate the kinetics and equilibrium exchange behaviour of sodium ions; difference between using linear least squares (LLS) and non-linear least squares (NLLS) methods for data interpretation; and, effect of changing the type of anion in solution which accompanied the sodium species. Kinetic studies suggested that the exchange process was best described by a pseudo first order rate expression based upon non-linear least squares analysis of the test data. Application of the Langmuir Vageler isotherm model was recommended as it allowed confirmation that experimental conditions were sufficient for maximum loading of sodium ions to occur. The Freundlich expression best fitted the equilibrium data when analysing the information by a NLLS approach. In contrast, LLS methods suggested that the Langmuir model was optimal for describing the equilibrium process. The Competitive Langmuir model which considered the stoichiometric nature of ion exchange process, estimated the maximum loading of sodium ions to be 64.7 g Na/kg resin. This latter value was comparable to sodium ion capacities for SAC resin published previously. Inherent discrepancies involved when using linearized versions of kinetic and isotherm equations were illustrated, and despite their widespread use, the value of this latter approach was questionable. The equilibrium behaviour of sodium ions form sodium fluoride solution revealed that the sodium ions were now more preferred by the resin compared to the situation with sodium chloride. The solution chemistry of hydrofluoric acid was suggested as promoting the affinity of the sodium ions to the resin.

BDST modelling of sodium ion exchange column behaviour with strong acid cation resin in relation to coal seam water treatment

Reverse osmosis is the dominant technology utilized for desalination of saline water produced during the extraction of coal seam gas. Alternatively, ion exchange is of interest due to potential cost advantages. However, there is limited information regarding the column performance of strong acid cation resin for removal of sodium ions from both model and actual coal seam water samples. In particular, the impact of bed depth, flow rate, and regeneration was not clear. Consequently, this study applied Bed Depth Service Time (BDST) models to reveal that increasing sodium ion concentration and flow rates diminished the time required for breakthrough to occur. The loading of sodium ions on fresh resin was calculated to be ca. 71.1 g Na/kg resin. Difficulties in regeneration of the resin using hydrochloric acid solutions were discovered, with 86% recovery of exchange sites observed. The maximum concentration of sodium ions in the regenerant brine was found to be 47,400 mg/L under the conditions employed. The volume of regenerant waste formed was 6.2% of the total volume of water treated. A coal seam water sample was found to load the resin with only 53.5 g Na/kg resin, which was consistent with not only the co-presence of more favoured ions such as calcium, magnesium, barium and strontium, but also inefficient regeneration of the resin prior to the coal seam water test.

Ion exchange of sodium chloride and sodium bicarbonate solutions using strong acid cation resins in relation to coal seam water treatment

Coal seam gas production has resulted in the production of large volumes of associated water which contains dissolved salts dominated by sodium chloride and sodium bicarbonate. Ion exchange using synthetic resins has been proposed as a method for desalination of coal seam water to make it suitable for various beneficial reuse options. This study investigated the behaviour of solutions of sodium chloride and sodium bicarbonate with respect to exchange with Lanxess S108H strong acid cation (SAC) resin. Equilibrium isotherms were created for solutions of NaCl and NaHCO3 and an actual sample of coal seam water from the Surat Basin in southern Queensland. The exchange of sodium ions arising from sodium bicarbonate was found to be considerably more favourable than exchange of sodium ions from sodium chloride solutions. This latter behaviour was attributed to the secondary decomposition of bicarbonate species under acidic conditions which resulted in the evolution of carbon dioxide and formation of water. The isotherm profiles could not be satisfactorily fitted by a single isotherm model such as the Langmuir expression. Instead, two Langmuir equations had to be simultaneously applied in order to fit the sections of the isotherm attributable to sodium ion exchange from sodium bicarbonate and sodium chloride. The shape of the isotherm profile was dependent upon the ratio of sodium chloride to sodium bicarbonate in solution and there was a high degree of correlation between simulated and actual coal seam water solutions.

Exploration of the fundamental equilibrium behaviour of calcium exchange with weak acid cation resins

This study evaluated the complexity of calcium ion exchange with sodium exchanged weak acid cation resin (DOW MAC-3). Exchange equilibria recorded for a range of different solution normalities revealed profiles which were represented by conventional “L” or “H” type isotherms at low values of equilibrium concentration (Ce) of calcium ions, plus a superimposed region of increasing calcium uptake was observed at high Ce values. The loading of calcium ions was determined to be ca. 53.5 to 58.7 g/kg of resin when modelling only the sorption curve created at low Ce values,which exhibited a well-defined plateau. The calculated calcium ion loading capacity for DOWMAC-3 resin appeared to correlate with the manufacturer's recommendation. The phenomenon of super equivalent ion exchange (SEIX) was observed when the “driving force” for the exchange process was increased in excess of 2.25 mmol calcium ions per gram of resin in the starting solution. This latter event was explained in terms of displacement of sodium ions from sodium hydroxide solution which remained in the resin bead following the initial conversion of the as supplied “H+” exchanged resin sites to the “Na+” version required for softening studies. Evidence for hydrolysis of a small fraction of the sites on the sodium exchanged resin surface was noted. The importance of carefully choosing experimental parameters was discussed especially in relation to application of the Langmuir–Vageler expression. This latter model which compared the ratio of the initial calcium ion concentration in solution to resin mass, versus final equilibrium loading of the calcium ions on the resin; was discovered to be an excellent means of identifying the progress of the calcium–sodium ion exchange process. Moreover, the Langmuir–Vageler model facilitated standardization of various calcium–sodium ion exchange experiments which allowed systematic experimental design.

Adsorption Isotherms for Removal of Linoleic Acid from Ethanolic Solutions Using the Strong Anion Exchange Resin Amberlyst A26 OH

Adsorption isotherms for the removal of linoleic acid from aqueous ethanol were measured using a strong anion exchange resin (Amberlyst A26 OH). The data for linoleic acid were compared with previously published results for oleic acid. The equilibrium data were correlated using the Langmuir and Freundlich isotherms. Lower average deviations between experimental and calculated results were obtained with the Langmuir model. The capacity of the resin for adsorbing linoleic acid was evaluated at different water contents in ethanol, 100 w = 0.50 to 15.27, and at 298.15 K. The water content in ethanol does not influence significantly the equilibrium behavior, and the strong anion exchange resin has a good performance in the removal of linoleic acid from the liquid phase.

Sulfated fibrous ZrO2/Al2O3 core and shell nanocomposites : a novel strong acid catalyst with hierarchically macro-mesoporous nanostructure

A series of solid strong acid catalysts were synthesised from fibrous ZrO2/Al2O3 core and shell nanocomposites. In this series, the zirconium molar percentage was varied from 2 % to 50 %. The ZrO2/Al2O3 nanocomposites and their solid strong acid counterparts were characterised by a variety of techniques including 27Al magic angle spinning nuclear magnetic resonance (MAS-NMR), scanned electronic microscopy (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), Nitrogen adsorption and infrared emission spectroscopy (IES). NMR results show that the interaction between zirconia species and alumina strongly correlates with pentacoordinated aluminium sites. This can also be detected by the change in binding energy of the 3d electrons of the zirconium. The acidity of the obtained solid acids was tested by using them as catalysts for the benzolyation of toluene. It was found that a sample with a 50 % zirconium molar percentage possessed the highest surface acidity equalling that of pristine sulfated zirconia despite the reduced mass of zirconia.

Development of an Analytical Methodology for Quantification of Strong Acid in Diesel Oil

Many factors can affect the quality of diesel oil, in particular the degradation processes that are directly related to some organosulfur compounds. During the degradation process, these compounds are oxidized into their corresponding sulfonic acids, generating a strong acid content during the process. p-Toluene sulfonic acid analysis was performed using the linear sweep voltammetry technique with a platinum ultramicroelectrode in aqueous solution containing 3 mol L(-1) potassium chloride. An extraction step was introduced prior to the voltammetric detection in order to avoid the adsorption of organic molecules, which inhibit the electrochemical response. The extraction step promoted the transference of sulfonic acid from the diesel oil to an aqueous phase. The method was accurate and reproducible, with detection and quantification limits of 5 ppm and 15 ppm, respectively. Recovery of sulfonic acid was around 90%.

DEVELOPMENT OF ION EXCHANGE MODELS FOR WATER TREATMENT AND APPLICATION TO THE INTERNATIONAL SPACE STATION WATER PROCESSOR

The International Space Station (ISS) requires a substantial amount of potable water for use by the crew. The economic and logistic limitations of transporting the vast amount of water required onboard the ISS necessitate onboard recovery and reuse of the aqueous waste streams. Various treatment technologies are employed within the ISS water processor to render the waste water potable, including filtration, ion exchange, adsorption, and catalytic wet oxidation. The ion exchange resins and adsorption media are combined in multifiltration beds for removal of ionic and organic compounds. A mathematical model (MFBMODEL™) designed to predict the performance of a multifiltration (MF) bed was developed. MFBMODEL consists of ion exchange models for describing the behavior of the different resin types in a MF bed (e.g., mixed bed, strong acid cation, strong base anion, and weak base anion exchange resins) and an adsorption model capable of predicting the performance of the adsorbents in a MF bed. Multicomponent ion exchange ii equilibrium models that incorporate the water formation reaction, electroneutrality condition, and degree of ionization of weak acids and bases for mixed bed, strong acid cation, strong base anion, and weak base anion exchange resins were developed and verified. The equilibrium models developed use a tanks-inseries approach that allows for consideration of variable influent concentrations. The adsorption modeling approach was developed in related studies and application within the MFBMODEL framework was demonstrated in the Appendix to this study. MFBMODEL consists of a graphical user interface programmed in Visual Basic and Fortran computational routines. This dissertation shows MF bed modeling results in which the model is verified for a surrogate of the ISS waste shower and handwash stream. In addition, a multicomponent ion exchange model that incorporates mass transfer effects was developed, which is capable of describing the performance of strong acid cation (SAC) and strong base anion (SBA) exchange resins, but not including reaction effects. This dissertation presents results showing the mass transfer model's capability to predict the performance of binary and multicomponent column data for SAC and SBA exchange resins. The ion exchange equilibrium and mass transfer models developed in this study are also applicable to terrestrial water treatment systems. They could be applied for removal of cations and anions from groundwater (e.g., hardness, nitrate, perchlorate) and from industrial process waters (e.g. boiler water, ultrapure water in the semiconductor industry).

The influence of organic acids in relation to acid deposition in controlling the acidity of soil and stream waters on a seasonal basis

Much uncertainty still exists regarding the relative importance of organic acids in relation to acid deposition in controlling the acidity of soil and surface waters. This paper contributes to this debate by presenting analysis of seasonal variations in atmospheric deposition, soil solution and stream water chemistry for two UK headwater catchments with contrasting soils. Acid neutralising capacity (ANC), dissolved organic carbon (DOC) concentrations and the Na:Cl ratio of soil and stream waters displayed strong seasonal patterns with little seasonal variation observed in soil water pH. These patterns, plus the strong relationships between ANC, Cl and DOC, suggest that cation exchange and seasonal changes in the production of DOC and seasalt deposition are driving a shift in the proportion of acidity attributable to strong acid anions, from atmospheric deposition, during winter to predominantly organic acids in summer.

Adsorption of Pb(2+), Cu(2+) and Cd(2+) in FDU-1 silica and FDU-1 silica modified with humic acid

Ordered mesoporous silica with cubic structure, type FDU-1, was synthesized under strong acid media using B-50-6600 poly(ethylene oxide)-poly(butilene oxide)-poly(ethylene oxide) triblock copolymer (EO(39)BO(47)EO(39)) and tetraethyl orthosilicate (TEOS). Humic acid (HA) was modified to the synthesis process at a concentration of 1.5 mmol per gram of SiO(2). Thermogravimetry, small angle X-ray diffraction, nitrogen adsorption and high resolution transmission electron microscopy were used to characterize the samples. The pristine FDU-1 and FDU-1 with incorporated 1.5 mmol of HA were tested for adsorption of Pb(2+), Cu(2+) and Cd(2+) in aqueous solution. Incorporation of humic acid into the FDU-1 silica afforded an adsorbent with strong affinity for Cd(2+), Cu(2+) and Pb(2+) from single ion solutions. Adsorption of Cu(2+) was significantly enhanced after incorporation of humic acid, a fact that can be explained by the formation of complexes with carboxylic and phenolic groups at low concentrations of the metal cation. The results demonstrated the potential applicability of FDU-1 with incorporated HA in the removal of low concentrations of heavy metal cations from aqueous solution, such as wastewaters, after usual precipitation of metal hydroxides in alkaline medium and proper pH conditioning in the range between 6 and 7. (C) 2007 Elsevier Inc. All rights reserved.

The impact of hydrofluoric acid etching followed by unfilled resin on the biaxial strength of a glass-ceramic

Objectives: To evaluate the null hypotheses that hydrofluoric (HF) acid etching time would neither decrease the biaxial flexural strength of a glass-based veneering ceramic nor enhance it after silane and unfilled resin (UR) applications. Methods: Disc-shaped IPS e.max ZirPress specimens were allocated into 12 groups: G1-control (no-etching), G2-30 s, G3-60 s, G4-90 s, G5-120 s, G6-60 s + 60 s. Groups (G7-G12) were treated in the same fashion as G1-G6, but followed by silane and UR applications. Surface morphology and roughness (Ra and Rq) of the ceramics were assessed by means of scanning electron microscopy (SEM) and profilometry, respectively. Flexural strength was determined by biaxial testing. Data were analyzed by two-way ANOVA and the Sidak test (α = 0.05). Weibull statistics were estimated and finite element analysis (FEA) was carried out to verify the stress concentration end areas of fracture. Results: The interaction (etching time vs. surface treatment) was significant for Ra (p = 0.008) and Rq (0.0075). Resin-treated groups presented significantly lower Ra and Rq than non-treated groups, except for the 60 s group (p < 0.005). SEM revealed that etching affected the ceramic microstructure and that the UR was able to penetrate into the irregularities. A significant effect of etching time (p = 0.029) on flexural strength was seen. G7-G12 presented higher strength than G1-G6 (p < 0.0001). None of experimental groups failed to show 95% confidence intervals of σ 0 and m overlapped. FEA showed lower stress concentration after resin treatment. Significance: HF acid etching time did not show a damaging effect on the ceramic flexural strength. Moreover, the flexural strength could be enhanced after UR treatment. © 2013 Academy of Dental Materials.

Evaluation of ion exchange as a pre-treatment option for coal seam gas water

The Coal Seam Gas (CSG) industry in Australia has grown significantly in recent years. During the gas extraction process, water is also recovered which is brackish in character. In order to facilitate beneficial reuse of the water, the CSG industry has primarily invested in Reverse Osmosis (RO) as the primary method for associated water desalination. However, the presence of alkaline earth ions in the water combined with the inherent alkalinity of the water may result in RO membrane scaling. Consequently, weak acid cation (WAC) synthetic ion exchange resins were investigated as a potential solution to this potential problem. It was shown that resins were indeed highly efficient at treating single and multi-component solutions of alkaline earth ions. The interaction of the ions with the resin was found to be considerably more complex that previously reported.